WO2018228407A1 - Graphene/metal nanobelt composite conductive ink, preparation method therefor and application thereof - Google Patents

Graphene/metal nanobelt composite conductive ink, preparation method therefor and application thereof Download PDF

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WO2018228407A1
WO2018228407A1 PCT/CN2018/090975 CN2018090975W WO2018228407A1 WO 2018228407 A1 WO2018228407 A1 WO 2018228407A1 CN 2018090975 W CN2018090975 W CN 2018090975W WO 2018228407 A1 WO2018228407 A1 WO 2018228407A1
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graphene
conductive ink
resin
metal
metal nanobelt
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PCT/CN2018/090975
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French (fr)
Chinese (zh)
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陈宜波
魏岚
庄江强
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厦门信达光电物联科技研究院有限公司
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Publication of WO2018228407A1 publication Critical patent/WO2018228407A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/104—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

  • the invention relates to a graphene conductive ink for electronic industry and a preparation method and application thereof, in particular to a graphene/metal nanobelt composite conductive ink for manufacturing an electronic circuit for electronic industry and a preparation method thereof.
  • Conductive lines and conductive electrodes are generally prepared in the electronics industry using conductive pastes, conductive pastes, conductive coatings, and conductive inks. Such materials generally use metal powder as a conductive filler, and the metal materials used include gold, silver, copper, nickel, aluminum, iron, and the like. Among them, conductive silver paste is the most widely used.
  • the main application fields include printed circuit board (PCB), display device (OLED, touch screen), RFID antenna, sensor electrode, solar cell electrode, printed battery, super capacitor, solid state. Battery electrodes, etc.
  • PCB printed circuit board
  • OLED organic light-ray
  • RFID antenna RF antenna
  • sensor electrode solar cell electrode
  • printed battery super capacitor
  • solid state solid state.
  • Battery electrodes etc.
  • screen printing technology some traditional thick film conductive pastes have been widely used in PCBs, automotive heaters, electromagnetic shields and membrane switches.
  • the preparation cost is high, and the volume resistance changes after the aging test is large, thereby limiting the application field of the product.
  • Patent No. 104263082A discloses a graphene organic silver conductive ink and a preparation method thereof.
  • Patent No. CN104292984A discloses a method for fabricating a graphene ink and a graphene line.
  • the prepared ink has a viscosity of more than 100 cp, and a patterned graphene line is obtained by using a masking, ink spraying, curing and removing step.
  • Patent No. 104263082A discloses a graphene organic silver conductive ink and a preparation method thereof.
  • Patent No. CN104292984A discloses a method for fabricating a graphene ink and a graphene line.
  • the prepared ink has a viscosity of more than 100 cp, and a patterned graphene line is obtained by using a masking, ink spraying, curing and removing step.
  • CN103436099A discloses a composite conductive ink mainly comprising a mixture of flake silver powder and nano silver powder together with graphene and nano graphite flakes as a conductive filler, wherein the thickness of the flake silver powder is ⁇ 100 nm, and the D50 of the flake silver powder is 3- 7 ⁇ m, the particle size of the nano silver powder is ⁇ 100nm, and the mass ratio of the flake silver powder to the nano silver powder is (8-10):1.
  • Patent No. 201510582047.8 discloses a microcrystalline graphene conductive ink and a preparation method thereof.
  • the conductive ink is mainly obtained by adding microcrystalline graphite powder, an adhesion aid, a dispersing agent and the like into a ball mill tank for ball milling, and separating the ball mill beads to obtain the microcrystalline graphite.
  • Patent No. 201610343203.X discloses a composite conductive ink film and a preparation method thereof, wherein the ink is mainly composed of a mixture of flake silver powder and nano silver powder or flake silver powder, a mixture of graphene and graphene oxide, copper.
  • the conductive ink film slurry is mainly disposed, and a suitable amount of the copper metal layer is evaporated onto the substrate, and then the conductive ink paste is applied onto the substrate on which the copper metal layer is evaporated, and the composite conductive ink is cured.
  • Patent No. US 2011/0186786 A1 discloses a process for preparing an organic compound composite of a graphene sheet layer and at least one charged functional group, wherein the charged group includes an ammonium salt, a sulfate, a phosphate, a sulfonate or the like. No.
  • 8,278,757 B2 discloses a conductive layer ink for printed electronic devices consisting of functionalized graphene and at least one binder, which ink may optionally contain conductive components other than functionalized graphene, such as Metal particles (including metal alloys), conductive metal oxides, polymers, carbonaceous materials, and metal coating materials are also mainly characterized in that the composition of the conductive ink is functionalized graphene and high molecular PEO.
  • the conductive ink is prepared by using the graphene material alone, and it is difficult to obtain a highly dense conductive line, and the conductivity stability of the prepared conductive line cannot be ensured.
  • the use of graphene, flake silver powder and nano silver particles as composite conductive fillers requires the use of a large amount of silver material to achieve the purpose of improving conductivity, and the preparation cost of the conductive ink is high.
  • an object of the present invention is to provide a graphene/metal nanobelt composite conductive ink and a preparation method and application thereof, which reduce the precious metal content while improving conductivity.
  • a graphene/metal nanobelt composite conductive ink comprising the following components by weight: 1-20 parts of graphene, 1-5 parts of metal nanobelts, 1-20 parts of nano-conductive carbon black, graphite 0 ⁇ 20 parts, 1 to 25 parts of polymer resin, 0.5 to 10 parts of auxiliary agent, and 10 to 70 parts of solvent; wherein the metal nanobelt has a bandwidth of less than 200 nm, a belt length of 1 to 50 ⁇ m, and an aspect ratio of 10:1. 2500:1, thickness less than 100nm.
  • the total mass of the graphene, the metal nanobelt, the nanoconductive carbon black and the graphite is 10 to 35% of the total mass of the ink.
  • the metal nanobelt comprises at least one of a silver nanobelt, a copper nanobelt, a palladium nanobelt, a nickel nanobelt, a multi-component metal nanobelt subjected to surface organic modification or metal oxide modification treatment.
  • the graphite is one of natural dense crystalline graphite, natural flake graphite, natural cryptocrystalline graphite or microcrystalline graphite, expanded graphite, or a combination of two or more.
  • the metal nanobelt has a bandwidth of 10 to 100 nm, a tape length of 2 to 10 ⁇ m, an aspect ratio of 20:1 to 200:1, and a thickness of 5 to 50 nm.
  • the graphene is at least one of a single layer or 2 to 5 layers of graphene, reduced graphene oxide, graphene nanosheets, and graphene nanoribbons, and the sheet size is 2 to 50 ⁇ m, and the thickness thereof is 1 to 10 nm; wherein the reduced graphene oxide has a carbon to oxygen ratio of from 1000:1 to 2:1, more preferably from 1000:1 to 200:1.
  • the polymer binder resin in the polymer resin is a thermosetting adhesive, a thermoplastic adhesive, a rubber type adhesive or a composite adhesive;
  • the thermosetting adhesive is mainly made of a thermosetting resin containing a reactive group, and is thermoplastic.
  • the adhesive is mainly composed of a thermoplastic resin having a linear polymer structure, and the composite adhesive is mainly composed of a thermosetting resin, a synthetic rubber or a thermoplastic resin.
  • the polymer binder includes an epoxy resin, a phenol resin, a hydroxychloroacetic resin, a carboxy chloroacetate resin, an acrylic resin, a ternary hydroxy resin, a polyester resin, an ethyl cellulose, a propyl cellulose urethane resin. At least one of polyvinylidene fluoride resin, neoprene rubber, and nitrile rubber.
  • the solvent is at least one of an alcohol solvent, an ester solvent, an aromatic hydrocarbon solvent, a ketone solvent, an ether solvent, and an aliphatic alkane solvent.
  • the solvent includes ethanol, isopropanol, n-butanol, terpineol, tributyl phosphate, propylene glycol methyl ether propionate, diethylene glycol dibenzoate, N-methylpyrrolidone, dimethyl Carboxamide, diethylene glycol ethyl ether ethyl ester, ethylene glycol diglycidyl ether, ethylene glycol butyl ether acetate, DBE, propylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, toluene, xylene, acetone, At least one of cyclohexanone, ethylene glycol butyl ether, propylene glycol butyl ether, methyl cyclohexane, n-hexane, and #150 gasoline.
  • the metal nanoparticles are further contained in an amount of 0.1 to 5 parts by weight, and the metal nanoparticles are at least one of silver particles, copper particles, palladium particles, and nickel particles, and have a particle diameter of 10 to 100 nm.
  • the auxiliary agent includes at least one of an antifoaming agent, an adhesion promoter, a wetting agent, a leveling agent, a coupling agent, an emulsifier, and a drier.
  • a method for preparing the above graphene/metal nanobelt composite conductive ink comprises the following steps:
  • (d) Processing of conductive ink primary product The conductive ink primary product in (c) is placed in a container of a high-speed shear disperser for solid-liquid high-speed shear dispersion mixing or high-speed grinding mixing using a ball mill, and then transferred to three Grinding to a fineness of 5 to 10 ⁇ m in roll grinding gives a final product of a homogeneous conductive ink.
  • the above graphene/metal nanobelt composite conductive ink is applied to printed conductive lines.
  • the graphene/metal nanobelt composite conductive ink is printed on the substrate by screen printing, flexographic printing, gravure printing or inkjet printing.
  • the substrate includes a polyester (PET) substrate, a paper substrate, a fiber cloth substrate, a polyimide (PI) substrate, a crystalline silicon wafer, a flexible wiring board, a ceramic substrate, a PCB substrate, and the like.
  • the printed conductive circuit further comprises a process step of drying and heat-treating the conductive circuit printed on the substrate; wherein the heat treatment temperature ranges from 80 to 200 ° C, and the heat treatment time is from 5 to 240 minutes.
  • the drying heat treatment process includes single-stage drying or multi-stage drying.
  • the metal nanobelt material of the present invention has a micrometer-scale in the length direction, a nanometer to a nanometer-scale in the width and thickness direction, and has the dual characteristics of micrometers and nanomaterials, and the single metal nanobelt itself is an independent one.
  • the conductive network of the formed conductive pattern is more continuous than the combined filler of ordinary micron-sized metal particles and nano-sized metal particles.
  • the conductive line has more excellent denseness than the combined use of metal particles (spherical, spheroidal, etc.), and the conductivity of the conductive line can be further improved.
  • the present invention replaces the point contact of the common metal nanoparticles with the conductive filler by using the two-dimensional flake graphene and the metal nanobelt material in combination with the surface contact between the metal nanobelt and the graphene and the micro-nano carbon conductive filler.
  • the flat strip shape of the metal nanobelt penetrates between different conductive fillers to form a wire network, ensuring excellent electrical conductivity of the conductive trace.
  • the metal nanobelt material used in the present invention is a micro/nano material having a high specific surface area, and as an auxiliary material of the conductive filler, the nano-material has a large specific surface area and a small amount of metal is added as compared with the ordinary sheet metal conductive material.
  • the nanobelt can increase the surface contact between the graphene sheet and its surface contact with other granular conductive fillers, and can significantly improve the conductive effect of the conductive line.
  • the introduction of the metal nanobelt can significantly reduce the total amount of the conductive filler.
  • the addition amount of the noble metal conductive filler can be significantly reduced, and the preparation cost of the composite conductive ink can be reduced.
  • FIG. 1 is a schematic view showing the microscopic appearance of a conductive ink printed conductive line of the present invention.
  • the parts by weight of each raw material are as follows:
  • the primary conductive ink in (c) is placed in a container of a high-speed shear disperser for solid-liquid high-speed shear dispersion mixing for 1 hour, and then subjected to solid-liquid high-speed ball milling dispersion mixing 12 After an hour, it was transferred to a three-roll mill to a fineness of 10 ⁇ m, and the obtained homogeneous conductive ink was the final product No. 1.
  • the parts by weight of each raw material are as follows:
  • the primary conductive ink in (c) is placed in a container of a high-speed shear disperser for solid-liquid high-speed ball milling dispersion mixing for 12 hours, and then transferred to a three-roll mill for grinding to fine The degree reached 10 ⁇ m, and the obtained homogeneous conductive ink was the final No. 2 product.
  • the parts by weight of each raw material are as follows:
  • the primary conductive ink in (c) is placed in a container of a high-speed shear disperser for solid-liquid high-speed ball milling dispersion mixing for 24 hours, and then transferred to a three-roll mill for grinding to fine The degree reached 5 ⁇ m, and the obtained homogeneous conductive ink was the final No. 3 product.
  • the parts by weight of each raw material are as follows:
  • Graphene, nanocarbon black, organic modified silver nanobelt and silver nanoparticle powder are weighed according to a ratio of 10:7:3:1, and then uniformly mixed by high-speed stirring. And 3g dispersant HR4013 was added during the mixing process for modification treatment.
  • the graphene is reduced graphene oxide, and the carbon-oxygen ratio is 1000:1 to 200:1; the organic modified silver nanobelt has a bandwidth of 10 to 100 nm, a strip length of 2 to 10 ⁇ m, and a thickness of 5 to 50 nm.
  • the silver nanoparticles have a particle size of 20 nm.
  • the primary conductive ink in (c) is placed in a ball mill for solid-liquid high-speed ball milling dispersion mixing for 24 hours, and then transferred to a three-roll mill for grinding to a fineness of 5 ⁇ m.
  • the homogeneous conductive ink is the final product No. 4.
  • the parts by weight of each raw material are as follows:
  • the primary conductive ink in (c) is placed in a ball mill for solid-liquid high-speed ball milling dispersion mixing for 24 hours, and then transferred to a three-roll mill for grinding to a fineness of 5 ⁇ m.
  • the homogeneous conductive ink is the final product No. 5.
  • the parts by weight of each raw material are as follows:
  • the preparation steps of the conductive ink of the comparative example are as follows:
  • the primary conductive ink in (c) is placed in a container of a high-speed shear disperser for solid-liquid high-speed shear dispersion mixing for 1 hour, and then transferred to a three-roll mill for grinding to The fineness reaches 10 ⁇ m, and the obtained homogeneous conductive ink is the final No. 6 product.
  • the conductive inks Nos. 1 to 6 obtained in Examples 1 to 6 were printed on a substrate by screen printing, flexographic printing, gravure printing or ink jet printing, and the substrate comprises a polyester (PET) substrate. Paper substrate, fiber cloth substrate, polyimide (PI) substrate, crystalline silicon wafer, flexible wiring board, ceramic substrate, PCB substrate, and the like. Then, the conductive line is subjected to a drying heat treatment process; wherein the heat treatment temperature ranges from 80 to 200 ° C, and the heat treatment time is from 5 to 240 minutes.
  • the drying heat treatment process includes single-stage drying or multi-stage drying. For example, referring to the microscopic morphology of the conductive line prepared by the conductive ink of Embodiment 2 of FIG.
  • the two-dimensional flake graphene and the metal nanobelt material are combined, and the metal nanobelt is electrically conductive with graphene and micro-nano carbon.
  • the surface contact between the fillers replaces the point contact of the common metal nanoparticles with the conductive filler, and the flat strip shape of the metal nanobelts is used to form a wire network between the different conductive fillers to ensure excellent electrical conductivity of the conductive wires.
  • the performance of the product was tested (tested by the four-probe method, the film thickness of the test film was 25 um, and the measured resistance was the average of the three film samples). The comparison results are shown in Table 7:
  • Example Conductive agent content (%) Square resistance ( ⁇ / ⁇ ) Example 1 30 0.05 Example 2 30 0.04 Example 3 32 0.08 Example 4 twenty one 0.07 Example 5 27 0.06 Example 6 (Comparative) 40 12

Abstract

Disclosed in the present invention is a graphene/metal nanobelt composite conductive ink and a preparation method therefor, a conductive ink which may be printed into a highly conductive line is prepared by using graphene, a metal nanobelt and a nanocarbon black material as a mixture powder of a conductive filler, and by using a polymer resin as a binder. Compared with conventionally used graphene/metal particle composite conductive ink, said conductive ink has a reduced metal content and excellent electrical conductivity. The conductive ink is low cost, has a simple method, has good controllability, and has high practical value for the development of the printing electronics industry.

Description

一种石墨烯/金属纳米带复合导电油墨及其制备方法和应用Graphene/metal nanobelt composite conductive ink and preparation method and application thereof 技术领域Technical field
本发明涉及电子工业用石墨烯导电油墨及其制备方法和应用，特别是涉及一种用于印刷法制造电子工业用电子电路的石墨烯/金属纳米带复合导电油墨及其制备方法。The invention relates to a graphene conductive ink for electronic industry and a preparation method and application thereof, in particular to a graphene/metal nanobelt composite conductive ink for manufacturing an electronic circuit for electronic industry and a preparation method thereof.
背景技术Background technique
电子工业上一般使用导电胶、导电浆料、导电涂料和导电油墨制备导电线路和导电电极。这类材料一般采用金属粉末作为导电填料，所用金属材料包括金、银、铜、镍、铝、铁等。其中以导电银浆料的应用最为广泛，主要的应用领域包括印刷线路板(PCB)、显示设备(OLED、触控屏)、RFID天线、传感器电极、太阳能电池电极、印刷电池、超级电容器、固态电池电极等。借助丝网印刷技术，一些传统厚膜导电浆料已经在PCB、汽车加热器、电磁屏蔽罩和薄膜开关等方面得到大规模的应用。然而，由于贵金属银的价格居高不下，其制备成本高、老化试验后体积电阻变化大，从而限制了产品的应用领域。Conductive lines and conductive electrodes are generally prepared in the electronics industry using conductive pastes, conductive pastes, conductive coatings, and conductive inks. Such materials generally use metal powder as a conductive filler, and the metal materials used include gold, silver, copper, nickel, aluminum, iron, and the like. Among them, conductive silver paste is the most widely used. The main application fields include printed circuit board (PCB), display device (OLED, touch screen), RFID antenna, sensor electrode, solar cell electrode, printed battery, super capacitor, solid state. Battery electrodes, etc. With the help of screen printing technology, some traditional thick film conductive pastes have been widely used in PCBs, automotive heaters, electromagnetic shields and membrane switches. However, due to the high price of precious metal silver, the preparation cost is high, and the volume resistance changes after the aging test is large, thereby limiting the application field of the product.
现公开的导电油墨技术中：专利号104263082A公开了一种石墨烯有机银导电油墨及其制备方法。专利号CN104292984A公开了一种石墨烯油墨及石墨烯线路的制作方法，所制备油墨黏度大于100cp，采用遮蔽、油墨喷涂、固化和移除步骤获得图案化石墨烯线路。专利号CN103436099A公开了一种复合导电油墨，其主要由片状银粉与纳米银粉的混合物与石墨烯与纳米石墨片共同作为导电填料，其中片状银粉厚度<100nm，片状银粉的D50为3-7μm，纳米银粉粒径<100nm，片状银粉与纳米银粉的质量比为(8-10)：1。专利号201510582047.8公开了一种微晶石墨烯导电油墨及制备方法，该导电油墨主要由微晶石墨粉与黏合助剂、分散剂等加入球磨罐中进行球磨，分离球磨珠得到所述微晶石墨烯导电油墨。专利号201610343203.X公开了一种复合导电油墨膜及其制备方法，该方法所述油墨主要由片状银粉与纳米银粉的混合物或片状银粉，石墨烯与氧化石墨烯的混合物、铜组成，其制备方法中主要通过配置导电油墨膜浆料，并蒸镀合适量的铜金属层到基底上，再将导电油墨浆料涂覆到蒸镀有铜金属层的基底上，固化得到复合导电油墨膜。专利号US2011/0186786A1公开了一种由石墨烯片层和至少一种带电官能团的有机化合物复合材料的制备方法，其中的带电基团 包括铵盐、硫酸盐、磷酸盐、磺酸盐等。专利号US8278757B2公开了一种用于印刷电子器件的导电层墨水，其组成为功能化石墨烯与至少一种粘接剂，该墨水除了可以选择包含除了功能化石墨烯以外的导电组分，如金属颗粒(包括金属合金)、导电金属氧化物、高分子、碳质材料，以及金属包覆材料，其主要特征还在于导电墨水的组成为功能化石墨烯与高分子PEO。In the disclosed conductive ink technology: Patent No. 104263082A discloses a graphene organic silver conductive ink and a preparation method thereof. Patent No. CN104292984A discloses a method for fabricating a graphene ink and a graphene line. The prepared ink has a viscosity of more than 100 cp, and a patterned graphene line is obtained by using a masking, ink spraying, curing and removing step. Patent No. CN103436099A discloses a composite conductive ink mainly comprising a mixture of flake silver powder and nano silver powder together with graphene and nano graphite flakes as a conductive filler, wherein the thickness of the flake silver powder is <100 nm, and the D50 of the flake silver powder is 3- 7μm, the particle size of the nano silver powder is <100nm, and the mass ratio of the flake silver powder to the nano silver powder is (8-10):1. Patent No. 201510582047.8 discloses a microcrystalline graphene conductive ink and a preparation method thereof. The conductive ink is mainly obtained by adding microcrystalline graphite powder, an adhesion aid, a dispersing agent and the like into a ball mill tank for ball milling, and separating the ball mill beads to obtain the microcrystalline graphite. Alkene conductive ink. Patent No. 201610343203.X discloses a composite conductive ink film and a preparation method thereof, wherein the ink is mainly composed of a mixture of flake silver powder and nano silver powder or flake silver powder, a mixture of graphene and graphene oxide, copper. In the preparation method, the conductive ink film slurry is mainly disposed, and a suitable amount of the copper metal layer is evaporated onto the substrate, and then the conductive ink paste is applied onto the substrate on which the copper metal layer is evaporated, and the composite conductive ink is cured. membrane. Patent No. US 2011/0186786 A1 discloses a process for preparing an organic compound composite of a graphene sheet layer and at least one charged functional group, wherein the charged group includes an ammonium salt, a sulfate, a phosphate, a sulfonate or the like. No. 8,278,757 B2 discloses a conductive layer ink for printed electronic devices consisting of functionalized graphene and at least one binder, which ink may optionally contain conductive components other than functionalized graphene, such as Metal particles (including metal alloys), conductive metal oxides, polymers, carbonaceous materials, and metal coating materials are also mainly characterized in that the composition of the conductive ink is functionalized graphene and high molecular PEO.
以上技术中，单独使用石墨烯材料制备导电油墨，难以获得高致密性导电线路，无法确保所制备导电线路的导电性稳定性。使用石墨烯与片状银粉、纳米银颗粒作为复合导电填料，需要使用较多含量的银材料才能实现提高导电性的目的，导电油墨的制备成本较高。In the above technique, the conductive ink is prepared by using the graphene material alone, and it is difficult to obtain a highly dense conductive line, and the conductivity stability of the prepared conductive line cannot be ensured. The use of graphene, flake silver powder and nano silver particles as composite conductive fillers requires the use of a large amount of silver material to achieve the purpose of improving conductivity, and the preparation cost of the conductive ink is high.
发明内容Summary of the invention
针对上述问题，本发明的目的是提供一种石墨烯/金属纳米带复合导电油墨及其制备方法和应用，减少贵金属含量的同时提高了导电性。In view of the above problems, an object of the present invention is to provide a graphene/metal nanobelt composite conductive ink and a preparation method and application thereof, which reduce the precious metal content while improving conductivity.
本发明的技术方案是：The technical solution of the present invention is:
一种石墨烯/金属纳米带复合导电油墨，所述油墨包括以下重量份的组份：石墨烯1～20份，金属纳米带1～5份，纳米导电炭黑1～20份，石墨0～20份，高分子树脂1～25份，助剂0.5～10份，溶剂10～70份；其中所述金属纳米带的带宽小于200nm，带长为1～50μm，长宽比为10:1～2500:1，厚度小于100nm。A graphene/metal nanobelt composite conductive ink, the ink comprising the following components by weight: 1-20 parts of graphene, 1-5 parts of metal nanobelts, 1-20 parts of nano-conductive carbon black, graphite 0~ 20 parts, 1 to 25 parts of polymer resin, 0.5 to 10 parts of auxiliary agent, and 10 to 70 parts of solvent; wherein the metal nanobelt has a bandwidth of less than 200 nm, a belt length of 1 to 50 μm, and an aspect ratio of 10:1. 2500:1, thickness less than 100nm.
优选的，所述石墨烯、金属纳米带、纳米导电炭黑和石墨的总质量为所述油墨总质量的10～35％。Preferably, the total mass of the graphene, the metal nanobelt, the nanoconductive carbon black and the graphite is 10 to 35% of the total mass of the ink.
优选的，所述金属纳米带包括银纳米带、铜纳米带、钯纳米带、镍纳米带、经过表面有机改性或金属氧化物改性处理的多组分金属纳米带中的至少一种。石墨为天然致密结晶状石墨、天然鳞片石墨、天然隐晶质石墨或微晶石墨、膨胀石墨中的一种或两种或多种的组合物。Preferably, the metal nanobelt comprises at least one of a silver nanobelt, a copper nanobelt, a palladium nanobelt, a nickel nanobelt, a multi-component metal nanobelt subjected to surface organic modification or metal oxide modification treatment. The graphite is one of natural dense crystalline graphite, natural flake graphite, natural cryptocrystalline graphite or microcrystalline graphite, expanded graphite, or a combination of two or more.
优选的，所述金属纳米带的带宽为10～100nm，带长为2～10μm，长宽比为20:1～200:1，厚度为5～50nm。Preferably, the metal nanobelt has a bandwidth of 10 to 100 nm, a tape length of 2 to 10 μm, an aspect ratio of 20:1 to 200:1, and a thickness of 5 to 50 nm.
优选的，所述石墨烯为单层或2～5层石墨烯、还原氧化石墨烯、石墨烯纳米片、石墨烯纳米带中的至少一种，其片层大小为2～50μm，其厚度为1～10nm；其中所述还原氧化石墨烯的碳氧比为1000:1～2:1，更优选为1000:1～200:1。Preferably, the graphene is at least one of a single layer or 2 to 5 layers of graphene, reduced graphene oxide, graphene nanosheets, and graphene nanoribbons, and the sheet size is 2 to 50 μm, and the thickness thereof is 1 to 10 nm; wherein the reduced graphene oxide has a carbon to oxygen ratio of from 1000:1 to 2:1, more preferably from 1000:1 to 200:1.
优选的，所述高分子树脂中的高分子粘接剂树脂为热固性胶粘剂、热塑性胶粘剂、橡胶型胶粘剂或复合型胶粘剂；所述热固性胶粘剂以含有反应性基团的热固性树脂为 主体制成，热塑性胶粘剂以线型高分子结构的热塑性树脂为主体，复合型胶粘剂以热固性树脂和合成橡胶或热塑性树脂为主体制成。Preferably, the polymer binder resin in the polymer resin is a thermosetting adhesive, a thermoplastic adhesive, a rubber type adhesive or a composite adhesive; the thermosetting adhesive is mainly made of a thermosetting resin containing a reactive group, and is thermoplastic. The adhesive is mainly composed of a thermoplastic resin having a linear polymer structure, and the composite adhesive is mainly composed of a thermosetting resin, a synthetic rubber or a thermoplastic resin.
进一步，所述高分子粘接剂包括环氧树脂、酚醛树脂、羟基氯醋树脂、羧基氯醋树脂、丙烯酸树脂、三元羟基树脂、聚酯树脂、乙基纤维素、丙基纤维素聚氨酯树脂、聚偏氟乙烯树脂、氯丁橡胶、丁腈橡胶中的至少一种。Further, the polymer binder includes an epoxy resin, a phenol resin, a hydroxychloroacetic resin, a carboxy chloroacetate resin, an acrylic resin, a ternary hydroxy resin, a polyester resin, an ethyl cellulose, a propyl cellulose urethane resin. At least one of polyvinylidene fluoride resin, neoprene rubber, and nitrile rubber.
优选的，所述溶剂为醇类溶剂、酯类溶剂、芳香烃类溶剂、酮类溶剂、醚类溶剂以及脂肪族烷烃类溶剂中的至少一种。Preferably, the solvent is at least one of an alcohol solvent, an ester solvent, an aromatic hydrocarbon solvent, a ketone solvent, an ether solvent, and an aliphatic alkane solvent.
进一步，所述溶剂包括乙醇、异丙醇、正丁醇、松油醇、磷酸三丁酯、丙二醇甲醚丙酸酯、二乙二醇二苯甲酸酯、N-甲基吡咯烷酮、二甲基甲酰胺、二甘醇***乙酯、乙二醇二缩水甘油醚、乙二醇丁醚乙酸酯、DBE、丙二醇甲醚醋酸酯、乙二醇***醋酸酯、甲苯、二甲苯、丙酮、环己酮、乙二醇丁醚、丙二醇丁醚、甲基环己烷、正己烷、#150汽油的至少一种。Further, the solvent includes ethanol, isopropanol, n-butanol, terpineol, tributyl phosphate, propylene glycol methyl ether propionate, diethylene glycol dibenzoate, N-methylpyrrolidone, dimethyl Carboxamide, diethylene glycol ethyl ether ethyl ester, ethylene glycol diglycidyl ether, ethylene glycol butyl ether acetate, DBE, propylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, toluene, xylene, acetone, At least one of cyclohexanone, ethylene glycol butyl ether, propylene glycol butyl ether, methyl cyclohexane, n-hexane, and #150 gasoline.
优选的，还包括重量份为0.1～5份的金属纳米颗粒，所述金属纳米颗粒是银颗粒、铜颗粒、钯颗粒、镍颗粒中的至少一种，粒径为10～100nm。Preferably, the metal nanoparticles are further contained in an amount of 0.1 to 5 parts by weight, and the metal nanoparticles are at least one of silver particles, copper particles, palladium particles, and nickel particles, and have a particle diameter of 10 to 100 nm.
优选的，所述助剂包括消泡剂、附着力促进剂、润湿剂、流平剂、偶联剂、乳化剂、催干剂中的至少一种。Preferably, the auxiliary agent includes at least one of an antifoaming agent, an adhesion promoter, a wetting agent, a leveling agent, a coupling agent, an emulsifier, and a drier.
一种上述石墨烯/金属纳米带复合导电油墨的制备方法，包括以下步骤：A method for preparing the above graphene/metal nanobelt composite conductive ink comprises the following steps:
(a)导电填料的预处理：将石墨烯、炭黑、石墨、金属纳米带按照预设比例称量后混合均匀，并在混合过程中添加分散剂助剂进行改性处理；(a) Pretreatment of conductive filler: The graphene, carbon black, graphite, and metal nanobelts are weighed according to a preset ratio and uniformly mixed, and a dispersant auxiliary agent is added for modification treatment during the mixing process;
(b)有机相的配制：将预设份量的高分子粘接剂树脂与防沉淀剂树脂置于加热反应容器中，再添加溶剂润湿树脂，将混合物加热至40～100℃，恒温加热搅拌0.5～12小时，确保树脂完全溶解后，将消泡剂、附着力促进剂、润湿剂、流平剂、乳化剂、催干剂中的至少一种添加到有机液相中，搅拌至分散溶解均一，得到有机相溶液，冷却待用；(b) Preparation of organic phase: placing a predetermined amount of polymer binder resin and anti-precipitant resin in a heating reaction vessel, adding a solvent to wet the resin, heating the mixture to 40-100 ° C, heating at a constant temperature After 0.5 to 12 hours, after ensuring complete dissolution of the resin, at least one of an antifoaming agent, an adhesion promoter, a wetting agent, a leveling agent, an emulsifier, and a drier is added to the organic liquid phase, and stirred until dispersed. Dissolve homogeneously, obtain an organic phase solution, and cool for use;
(c)导电油墨初级产品的制备：将(a)中预处理的导电填料缓慢添加到(b)中的有机相溶液中，边添加边搅拌，确保导电填料粉体完全润湿、分散到有机相溶液中，待粉体分散均一时，得到导电油墨初级产品；(c) Preparation of conductive ink primary product: slowly add the conductive filler pretreated in (a) to the organic phase solution in (b), and stir while adding to ensure that the conductive filler powder is completely wetted and dispersed to the organic In the phase solution, when the powder is uniformly dispersed, a conductive ink primary product is obtained;
(d)导电油墨初级产品的加工处理：将(c)中的导电油墨初级产品置于高速剪切分散机的容器中进行固液高速剪切分散混合或采用球磨机高速研磨混合，然后转移至三辊研磨中研磨至细度达到5～10μm，得到均质导电油墨的最终产品。(d) Processing of conductive ink primary product: The conductive ink primary product in (c) is placed in a container of a high-speed shear disperser for solid-liquid high-speed shear dispersion mixing or high-speed grinding mixing using a ball mill, and then transferred to three Grinding to a fineness of 5 to 10 μm in roll grinding gives a final product of a homogeneous conductive ink.
上述石墨烯/金属纳米带复合导电油墨于印制导电线路上的应用。The above graphene/metal nanobelt composite conductive ink is applied to printed conductive lines.
优选的，所述石墨烯/金属纳米带复合导电油墨通过丝网印刷、柔性版印刷、凹版印刷或喷墨打印印制导电线路于基材上。基材包括聚酯(PET)基材、纸质基材、纤维布基材、聚酰亚胺(PI)基材、晶硅片、柔性线路板、陶瓷基板、PCB基板等。Preferably, the graphene/metal nanobelt composite conductive ink is printed on the substrate by screen printing, flexographic printing, gravure printing or inkjet printing. The substrate includes a polyester (PET) substrate, a paper substrate, a fiber cloth substrate, a polyimide (PI) substrate, a crystalline silicon wafer, a flexible wiring board, a ceramic substrate, a PCB substrate, and the like.
优选的，所述印制导电线路还包括将印制在基材上的导电线路进行烘干热处理的工艺步骤；其中的热处理温度范围为80～200℃，热处理时间为5～240分钟。烘干热处理的工艺包括单段烘干或多段烘干。Preferably, the printed conductive circuit further comprises a process step of drying and heat-treating the conductive circuit printed on the substrate; wherein the heat treatment temperature ranges from 80 to 200 ° C, and the heat treatment time is from 5 to 240 minutes. The drying heat treatment process includes single-stage drying or multi-stage drying.
本发明包括以下有益效果：The invention includes the following beneficial effects:
1、本发明的金属纳米带材料，其在长度方向为微米级、宽度和厚度方向为纳米至百纳米级，兼具有微米、纳米材料的双重特征，单条金属纳米带其本身就是一条独立的导电线路，与普通微米级金属颗粒和纳米级金属颗粒的组合填料相比，所形成的导电图案的导电网络更加连续。与组合使用金属颗粒(球状、类球状等)相比，导电线路具有更优异的密实性，能够进一步提高导电线路的导电性。1. The metal nanobelt material of the present invention has a micrometer-scale in the length direction, a nanometer to a nanometer-scale in the width and thickness direction, and has the dual characteristics of micrometers and nanomaterials, and the single metal nanobelt itself is an independent one. In the conductive line, the conductive network of the formed conductive pattern is more continuous than the combined filler of ordinary micron-sized metal particles and nano-sized metal particles. The conductive line has more excellent denseness than the combined use of metal particles (spherical, spheroidal, etc.), and the conductivity of the conductive line can be further improved.
2、本发明通过结合使用二维片状石墨烯与金属纳米带材料，借助金属纳米带与石墨烯及微纳米碳导电填料之间的面接触代替普通金属纳米颗粒与导电填料的点接触，利用金属纳米带的扁平长条形状，在不同导电填料之间贯通形成导线网络，确保导电线路具有优异的导电性。2. The present invention replaces the point contact of the common metal nanoparticles with the conductive filler by using the two-dimensional flake graphene and the metal nanobelt material in combination with the surface contact between the metal nanobelt and the graphene and the micro-nano carbon conductive filler. The flat strip shape of the metal nanobelt penetrates between different conductive fillers to form a wire network, ensuring excellent electrical conductivity of the conductive trace.
3、本发明使用金属纳米带材料是具有高比表面积的微纳米材料，作为导电填料的辅助材料，与普通片状金属导电材料相比，能够充分发挥纳米材料比表面积大的特性，添加少量金属纳米带，就能够增加其与石墨烯片层之间的面接触及其与其他颗粒状导电填料点面接触几率，可以显著提升导电线路的导电效果。金属纳米带的引入能够显著降低了导电填料总量，对于石墨烯/金属复合油墨，能够显著降低贵金属导电填料的添加量，能够降低复合导电油墨的制备成本。3. The metal nanobelt material used in the present invention is a micro/nano material having a high specific surface area, and as an auxiliary material of the conductive filler, the nano-material has a large specific surface area and a small amount of metal is added as compared with the ordinary sheet metal conductive material. The nanobelt can increase the surface contact between the graphene sheet and its surface contact with other granular conductive fillers, and can significantly improve the conductive effect of the conductive line. The introduction of the metal nanobelt can significantly reduce the total amount of the conductive filler. For the graphene/metal composite ink, the addition amount of the noble metal conductive filler can be significantly reduced, and the preparation cost of the composite conductive ink can be reduced.
以下结合附图和实施例对本发明做进一步说明，但本发明不局限于实施例。The invention will be further described below in conjunction with the drawings and embodiments, but the invention is not limited to the embodiments.
附图说明DRAWINGS
图1为本发明的导电油墨印制导电线路微观形貌示意图。1 is a schematic view showing the microscopic appearance of a conductive ink printed conductive line of the present invention.
具体实施方式detailed description
为使本发明的目的、技术方案和优点更加清楚，下面结合附图和实施例对本发明的进行详细的描述。The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
实施例1Example 1
在本实施例中，各原料的重量份如下表1：In this embodiment, the parts by weight of each raw material are as follows:
Figure PCTCN2018090975-appb-000001
Figure PCTCN2018090975-appb-000001
本发明提供的一种石墨烯/银纳米带复合导电油墨的制备步骤如下：The preparation steps of a graphene/silver nanobelt composite conductive ink provided by the invention are as follows:
(a)导电填料的预处理：将石墨烯、炭黑、银纳米带粉体按照6:20:4的比例称量后，采用高速搅拌方式混合均匀，并在混合过程中添加2g钛酸酯偶联剂S9031助剂进行改性处理。其中石墨烯的片层大小约为10μm，厚度约为2nm；银纳米带的带宽约为10nm，带长约为2μm，厚度约为5nm。(a) Pretreatment of conductive filler: Graphene, carbon black, and silver nanobelt powder are weighed in a ratio of 6:20:4, mixed uniformly by high-speed stirring, and 2 g of titanate is added during mixing. The coupling agent S9031 auxiliary agent is modified. The graphene has a sheet size of about 10 μm and a thickness of about 2 nm; the silver nanobelt has a bandwidth of about 10 nm, a strip length of about 2 μm, and a thickness of about 5 nm.
(b)有机载体的制备：将9g丙烯酸树脂、1g聚酰胺蜡(具体物质？)称量后置于加热反应容器中，再添加48g N-甲基吡咯烷酮与9g松油醇，将树脂润湿，并将混合物加热至50℃，恒温加热搅拌2小时，确保树脂完全溶解后，将0.5g消泡剂Airex900、0.5g附着力促进剂EL-9041？逐渐添加到油墨中，搅拌至分散溶解均一冷却待用。(b) Preparation of organic carrier: 9 g of acrylic resin, 1 g of polyamide wax (specific substance?) were weighed and placed in a heated reaction vessel, and then 48 g of N-methylpyrrolidone and 9 g of terpineol were added to wet the resin. And the mixture was heated to 50 ° C, heated and stirred for 2 hours, to ensure that the resin is completely dissolved, 0.5g defoamer Airex900, 0.5g adhesion promoter EL-9041? Gradually added to the ink, stirred until dispersed and dissolved, and cooled for use.
(c)导电油墨初级产品的制备：将(a)中预处理的导电填料缓慢添加到(b)中的有机载体中，边添加边搅拌，确保导电填料粉体完全润湿、分散到有机载体中，得到导电油墨的初级产品。(c) Preparation of a conductive ink primary product: the conductive filler pretreated in (a) is slowly added to the organic vehicle in (b), and stirred while being added to ensure complete wetting and dispersion of the conductive filler powder to the organic vehicle In the middle, a primary product of conductive ink is obtained.
(d)导电油墨初级产品的加工处理：将(c)中的初级导电油墨置于高速剪切分散机的容器中进行固液高速剪切分散混合1小时，再进行固液高速球磨分散混合12小时，然后转移至三辊研磨中研磨至细度达到10μm，得到的均质导电油墨为最终1号产品。(d) Processing of the conductive ink primary product: the primary conductive ink in (c) is placed in a container of a high-speed shear disperser for solid-liquid high-speed shear dispersion mixing for 1 hour, and then subjected to solid-liquid high-speed ball milling dispersion mixing 12 After an hour, it was transferred to a three-roll mill to a fineness of 10 μm, and the obtained homogeneous conductive ink was the final product No. 1.
实施例2Example 2
在本实施例中，各原料的重量份如下表2：In this embodiment, the parts by weight of each raw material are as follows:
Figure PCTCN2018090975-appb-000002
Figure PCTCN2018090975-appb-000002
本发明提供的一种石墨烯/银纳米带复合导电油墨的制备步骤如下：The preparation steps of a graphene/silver nanobelt composite conductive ink provided by the invention are as follows:
(a)导电填料的预处理：将石墨烯、纳米炭黑、天然鳞片石墨、金属氧化物修饰银纳米带粉体按照6:16:5:3的比例称量后，采用高速搅拌方式混合均匀，并在混合过程中添加2.5g分散剂BYK163进行改性处理。其中石墨烯的片层大小约为20μm，厚度约为5nm；金属氧化物修饰银纳米带的带宽约为100nm，带长约为10μm，厚度约为10nm。(a) Pretreatment of conductive filler: Graphene, nanocarbon black, natural flake graphite, metal oxide modified silver nanobelt powder are weighed according to a ratio of 6:16:5:3, and then uniformly mixed by high-speed stirring. And adding 2.5 g of dispersant BYK163 during the mixing process for modification. The graphene has a sheet size of about 20 μm and a thickness of about 5 nm; the metal oxide-modified silver nanobelt has a bandwidth of about 100 nm, a strip length of about 10 μm, and a thickness of about 10 nm.
(b)有机载体的制备：将6g羟基氯醋树脂、3g聚酯树脂、1g聚酰胺蜡称量后置于加热反应容器中，再添加40g环己酮、10g丙二醇甲醚醋酸酯、8g磷酸三丁酯，将树脂润湿，并将混合物加热至60℃，恒温加热搅拌1小时，确保树脂完全溶解后,将0.5g消泡剂KS66、0.5g附着力促进剂EL9041、0.5g流平剂DC57逐渐添加到有机液相中，冷却待用；(b) Preparation of organic carrier: 6 g of hydroxychloroacetic acid resin, 3 g of polyester resin, 1 g of polyamide wax were weighed and placed in a heating reaction vessel, and then 40 g of cyclohexanone, 10 g of propylene glycol methyl ether acetate, and 8 g of phosphoric acid were added. Tributyl ester, the resin is wetted, and the mixture is heated to 60 ° C, heated and stirred at constant temperature for 1 hour, to ensure that the resin is completely dissolved, 0.5 g of defoamer KS66, 0.5g adhesion promoter EL9041, 0.5g leveling agent DC57 is gradually added to the organic liquid phase and cooled for use;
(c)导电油墨初级产品的制备：将(a)中预处理的导电填料缓慢添加到(b)中的有机载体中，边添加边搅拌，确保导电填料粉体完全润湿、分散到有机载体中，搅拌至分散溶解均一，得到导电油墨的初级产品。(c) Preparation of a conductive ink primary product: the conductive filler pretreated in (a) is slowly added to the organic vehicle in (b), and stirred while being added to ensure complete wetting and dispersion of the conductive filler powder to the organic vehicle The mixture is stirred until dispersed and dissolved to obtain a primary product of the conductive ink.
(d)导电油墨初级产品的加工处理：将(c)中的初级导电油墨置于高速剪切分散机的容器中进行固液高速球磨分散混合12小时，然后转移至三辊研磨中研磨至细度达到10μm，得到的均质导电油墨为最终2号产品。(d) Processing of the conductive ink primary product: the primary conductive ink in (c) is placed in a container of a high-speed shear disperser for solid-liquid high-speed ball milling dispersion mixing for 12 hours, and then transferred to a three-roll mill for grinding to fine The degree reached 10 μm, and the obtained homogeneous conductive ink was the final No. 2 product.
实施例3Example 3
在本实施例中，各原料的重量份如下表3：In this embodiment, the parts by weight of each raw material are as follows:
Figure PCTCN2018090975-appb-000003
Figure PCTCN2018090975-appb-000003
本发明提供的一种基于石墨烯/钯纳米带的复合导电油墨的制备步骤如下：The preparation steps of a graphene/palladium nanobelt-based composite conductive ink provided by the invention are as follows:
(a)导电填料的预处理：将石墨烯、纳米炭黑、天然微晶石墨、金属氧化物修饰钯纳米带粉体按照7:4:16:5的比例称量后，采用高速搅拌方式混合均匀，并在混合过程中添加3g分散剂KBM9103进行改性处理。其中石墨烯的片层大小约为5μm，厚度约为2nm；金属氧化物修饰钯纳米带的带宽约为150nm，带长约为20μm，厚度约为30nm。(a) Pretreatment of conductive filler: Graphene, nanocarbon black, natural microcrystalline graphite, metal oxide modified palladium nanobelt powder are weighed according to a ratio of 7:4:16:5, and then mixed by high-speed stirring. It was uniform, and 3 g of dispersant KBM9103 was added for modification treatment during the mixing. The graphene has a sheet size of about 5 μm and a thickness of about 2 nm; the metal oxide-modified palladium nanoribbon has a bandwidth of about 150 nm, a strip length of about 20 μm, and a thickness of about 30 nm.
(b)有机载体的制备：将4g聚偏氟乙烯树脂、10g聚酯树脂、1g聚酰胺蜡称量后置于加热反应容器中，再添加9g#150汽油、35g乙二醇***醋酸酯、4g柠檬酸三丁酯，将树脂润湿，并将混合物加热至60℃，恒温加热搅拌1小时，确保树脂完全溶解后，将0.5g消泡剂Airex900、1g附着力促进剂EL9041、0.5g流平剂DC57逐渐添加到有机液相中，冷却待用；(b) Preparation of organic carrier: 4 g of polyvinylidene fluoride resin, 10 g of polyester resin, 1 g of polyamide wax were weighed and placed in a heating reaction vessel, and then 9 g of #150 gasoline, 35 g of ethylene glycol ethyl ether acetate, 4g of tributyl citrate, the resin is wetted, and the mixture is heated to 60 ° C, heated and stirred at constant temperature for 1 hour, to ensure that the resin is completely dissolved, 0.5g of defoamer Airex900, 1g adhesion promoter EL9041, 0.5g flow The flat agent DC57 is gradually added to the organic liquid phase and cooled for use;
(c)导电油墨初级产品的制备：将(a)中预处理的导电填料缓慢添加到(b)中的有机载体中，边添加边搅拌，确保导电填料粉体完全润湿、分散到有机载体中，搅拌至分散溶解均一，得到导电油墨的初级产品。(c) Preparation of a conductive ink primary product: the conductive filler pretreated in (a) is slowly added to the organic vehicle in (b), and stirred while being added to ensure complete wetting and dispersion of the conductive filler powder to the organic vehicle The mixture is stirred until dispersed and dissolved to obtain a primary product of the conductive ink.
(d)导电油墨初级产品的加工处理：将(c)中的初级导电油墨置于高速剪切分散机的容器中进行固液高速球磨分散混合24小时，然后转移至三辊研磨中研磨至细度达到5μm，得到的均质导电油墨为最终3号产品。(d) Processing of the conductive ink primary product: the primary conductive ink in (c) is placed in a container of a high-speed shear disperser for solid-liquid high-speed ball milling dispersion mixing for 24 hours, and then transferred to a three-roll mill for grinding to fine The degree reached 5 μm, and the obtained homogeneous conductive ink was the final No. 3 product.
实施例4Example 4
在本实施例中，各原料的重量份如下表4：In this embodiment, the parts by weight of each raw material are as follows:
Figure PCTCN2018090975-appb-000004
Figure PCTCN2018090975-appb-000004
本发明提供的一种石墨烯/银纳米带的复合导电油墨的制备步骤如下：The preparation steps of the graphene/silver nanobelt composite conductive ink provided by the invention are as follows:
(a)导电填料的预处理：将石墨烯、纳米炭黑、有机改性银纳米带和银纳米颗粒粉体按照10:7:3:1的比例称量后，采用高速搅拌方式混合均匀，并在混合过程中添加3g分散剂HR4013进行改性处理。其中石墨烯为还原氧化石墨烯，碳氧比为1000:1～200:1；有机改性银纳米带的带宽为10～100nm，带长为2～10μm，厚度为5～50nm。银纳米颗粒的粒度为20nm。(a) Pretreatment of conductive filler: Graphene, nanocarbon black, organic modified silver nanobelt and silver nanoparticle powder are weighed according to a ratio of 10:7:3:1, and then uniformly mixed by high-speed stirring. And 3g dispersant HR4013 was added during the mixing process for modification treatment. The graphene is reduced graphene oxide, and the carbon-oxygen ratio is 1000:1 to 200:1; the organic modified silver nanobelt has a bandwidth of 10 to 100 nm, a strip length of 2 to 10 μm, and a thickness of 5 to 50 nm. The silver nanoparticles have a particle size of 20 nm.
(b)有机载体的制备：将4g羟基氯醋树脂、10g丙烯酸树脂、1g聚酰胺蜡称量后置于加热反应容器中，再添加24g N-甲基吡咯烷酮、35g乙醇将树脂润湿，并将混合物加热至50℃，恒温加热搅拌10小时，确保树脂完全溶解后，将0.5g消泡剂KS66、1g附着力促进剂EL9041、0.5g流平剂DC57逐渐添加到有机液相中，冷却待用；(b) Preparation of organic carrier: 4 g of hydroxychloroacetic acid resin, 10 g of acrylic resin, 1 g of polyamide wax were weighed and placed in a heating reaction vessel, and then 24 g of N-methylpyrrolidone and 35 g of ethanol were added to wet the resin. The mixture was heated to 50 ° C, heated and stirred at a constant temperature for 10 hours to ensure that the resin was completely dissolved, 0.5 g of antifoaming agent KS66, 1 g of adhesion promoter EL 9041, 0.5 g of leveling agent DC57 was gradually added to the organic liquid phase, and cooled. use;
(c)导电油墨初级产品的制备：将(a)中预处理的导电填料缓慢添加到(b)中的有机载体中，边添加边搅拌，确保导电填料粉体完全润湿、分散到有机载体中，搅拌至分散溶解均一，得到导电油墨的初级产品。(c) Preparation of a conductive ink primary product: the conductive filler pretreated in (a) is slowly added to the organic vehicle in (b), and stirred while being added to ensure complete wetting and dispersion of the conductive filler powder to the organic vehicle The mixture is stirred until dispersed and dissolved to obtain a primary product of the conductive ink.
(d)导电油墨初级产品的加工处理：将(c)中的初级导电油墨置于球磨机中进行固液高速球磨分散混合24小时，然后转移至三辊研磨中研磨至细度达到5μm，得到的均质导电油墨为最终4号产品。(d) processing of the conductive ink primary product: the primary conductive ink in (c) is placed in a ball mill for solid-liquid high-speed ball milling dispersion mixing for 24 hours, and then transferred to a three-roll mill for grinding to a fineness of 5 μm. The homogeneous conductive ink is the final product No. 4.
实施例5Example 5
在本实施例中，各原料的重量份如下表5：In the present embodiment, the parts by weight of each raw material are as follows:
Figure PCTCN2018090975-appb-000005
Figure PCTCN2018090975-appb-000005
本发明提供的一种基于石墨烯/纳米带的复合导电油墨的制备步骤如下：The preparation steps of a graphene/nanobelt-based composite conductive ink provided by the invention are as follows:
(a)导电填料的预处理：将石墨烯、纳米炭黑、膨胀石墨、铜纳米带和镍纳米带粉体按照7:4:12:2:2的比例称量后，采用高速搅拌方式混合均匀，并在混合过程中添加3g分散剂BYK333进行改性处理。其中石墨烯为还原氧化石墨烯，碳氧比为1000：1～200:1；铜纳米带的带宽为10～100nm，带长为2～10μm，厚度为5～50nm；镍纳米带的带宽为10～100nm，带长为2～10μm，厚度为5～50nm。(a) Pretreatment of conductive filler: Graphene, nanocarbon black, expanded graphite, copper nanobelt and nickel nanobelt powder are weighed according to a ratio of 7:4:12:2:2, and then mixed by high-speed stirring. It was uniform and modified by adding 3 g of dispersant BYK333 during the mixing process. The graphene is reduced graphene oxide, the carbon-oxygen ratio is 1000:1 to 200:1; the copper nanobelt has a bandwidth of 10 to 100 nm, the strip length is 2 to 10 μm, and the thickness is 5 to 50 nm; the bandwidth of the nickel nanobelt is 10 to 100 nm, a tape length of 2 to 10 μm, and a thickness of 5 to 50 nm.
(b)有机载体的制备：将4g羟基氯醋树脂、10g丙烯酸树脂、1g聚酰胺蜡称量后置于加热反应容器中，再添加18g N-甲基吡咯烷酮、35g乙醇将树脂润湿，并将混合物加热至50℃，恒温加热搅拌10小时，确保树脂完全溶解后，将0.5g消泡剂Airex900、1g附着力促进剂EL9041、0.5g流平剂DC57逐渐添加到有机液相中，冷却待用；(b) Preparation of organic carrier: 4 g of hydroxychloroacetic acid resin, 10 g of acrylic resin, 1 g of polyamide wax were weighed and placed in a heating reaction vessel, and 18 g of N-methylpyrrolidone and 35 g of ethanol were added to wet the resin. The mixture was heated to 50 ° C, heated and stirred at a constant temperature for 10 hours to ensure that the resin was completely dissolved, 0.5 g of antifoaming agent Airex 900, 1 g of adhesion promoter EL 9041, 0.5 g of leveling agent DC57 was gradually added to the organic liquid phase, and cooled. use;
(c)导电油墨初级产品的制备：将(a)中预处理的导电填料缓慢添加到(b)中的有机载体中，边添加边搅拌，确保导电填料粉体完全润湿、分散到有机载体中，搅拌至分散溶解均一，得到导电油墨的初级产品。(c) Preparation of a conductive ink primary product: the conductive filler pretreated in (a) is slowly added to the organic vehicle in (b), and stirred while being added to ensure complete wetting and dispersion of the conductive filler powder to the organic vehicle The mixture is stirred until dispersed and dissolved to obtain a primary product of the conductive ink.
(d)导电油墨初级产品的加工处理：将(c)中的初级导电油墨置于球磨机中进行固液高速球磨分散混合24小时，然后转移至三辊研磨中研磨至细度达到5μm，得到的均质导电油墨为最终5号产品。(d) processing of the conductive ink primary product: the primary conductive ink in (c) is placed in a ball mill for solid-liquid high-speed ball milling dispersion mixing for 24 hours, and then transferred to a three-roll mill for grinding to a fineness of 5 μm. The homogeneous conductive ink is the final product No. 5.
实施例6(对比实施例)Example 6 (Comparative Example)
在本实施例中，各原料的重量份如下表6：In this embodiment, the parts by weight of each raw material are as follows:
Figure PCTCN2018090975-appb-000006
Figure PCTCN2018090975-appb-000006
对比实施例的导电油墨的制备步骤如下：The preparation steps of the conductive ink of the comparative example are as follows:
(a)导电填料的预处理：将石墨烯、纳米炭黑、天然微晶石墨粉体按照12:20:18的比例称量后，采用高速搅拌方式混合均匀，并在混合过程中添加5g钛酸酯偶联剂S9031进行改性处理。(a) Pretreatment of conductive filler: Graphene, nanocarbon black, and natural microcrystalline graphite powder are weighed according to a ratio of 12:20:18, then uniformly mixed by high-speed stirring, and 5 g of titanium is added during the mixing process. The acid ester coupling agent S9031 is subjected to a modification treatment.
(b)有机载体的制备：将0.5g聚偏氟乙烯树脂2g、8g羧基氯醋树脂、1g聚酰胺蜡称量后置于加热反应容器中，再添加7g DBE溶剂、30g松油醇、5g，将树脂润湿，并将混合物加热至60℃，恒温加热搅拌1小时，确保树脂完全溶解后，将0.5g消泡剂Airex900、1g附着力促进剂EL9041、0.5g流平剂DC57逐渐添加到有机液相中，冷却待用；(b) Preparation of organic carrier: 0.5 g of polyvinylidene fluoride resin, 8 g of carboxychloroacetic resin, 1 g of polyamide wax were weighed and placed in a heating reaction vessel, and then 7 g of DBE solvent, 30 g of terpineol, 5 g were added. , the resin is wetted, and the mixture is heated to 60 ° C, heated and stirred at constant temperature for 1 hour, to ensure that the resin is completely dissolved, 0.5 g of defoamer Airex900, 1g adhesion promoter EL9041, 0.5g leveling agent DC57 is gradually added to In the organic liquid phase, cooling is used;
(c)导电油墨初级产品的制备：将(a)中预处理的导电填料缓慢添加到(b)中的有机载体中，边添加边搅拌，确保导电填料粉体完全润湿、分散到有机载体中，搅拌至分散溶解均一，得到导电油墨的初级产品。(c) Preparation of a conductive ink primary product: the conductive filler pretreated in (a) is slowly added to the organic vehicle in (b), and stirred while being added to ensure complete wetting and dispersion of the conductive filler powder to the organic vehicle The mixture is stirred until dispersed and dissolved to obtain a primary product of the conductive ink.
(d)导电油墨初级产品的加工处理：将(c)中的初级导电油墨置于高速剪切分散机的容器中进行固液高速剪切分散混合1小时，然后转移至三辊研磨中研磨至细度达到10μm，得到的均质导电油墨为最终6号产品。(d) Processing of the conductive ink primary product: the primary conductive ink in (c) is placed in a container of a high-speed shear disperser for solid-liquid high-speed shear dispersion mixing for 1 hour, and then transferred to a three-roll mill for grinding to The fineness reaches 10 μm, and the obtained homogeneous conductive ink is the final No. 6 product.
应用实施例Application example
将实施例1～6得到的导电油墨1～6号产品通过丝网印刷、柔性版印刷、凹版印刷 或喷墨打印印制导电线路于基材上，基材包括聚酯(PET)基材、纸质基材、纤维布基材、聚酰亚胺(PI)基材、晶硅片、柔性线路板、陶瓷基板、PCB基板等。然后，对导电线路进行烘干热处理的工艺步骤；其中的热处理温度范围为80～200℃，热处理时间为5～240分钟。烘干热处理的工艺包括单段烘干或多段烘干。举例来说，参考图1实施例2的导电油墨制得的导电线路的微观形貌，通过结合使用二维片状石墨烯与金属纳米带材料，借助金属纳米带与石墨烯及微纳米碳导电填料之间的面接触代替普通金属纳米颗粒与导电填料的点接触，利用金属纳米带的扁平长条形状，在不同导电填料之间贯通形成导线网络，确保导电线路具有优异的导电性。对产品的性能进行测试(采用四探针法进行测试，测试薄膜样品膜厚为25um，所测方阻值为3个薄膜样品的测试平均值)，对比结果如表7所示：The conductive inks Nos. 1 to 6 obtained in Examples 1 to 6 were printed on a substrate by screen printing, flexographic printing, gravure printing or ink jet printing, and the substrate comprises a polyester (PET) substrate. Paper substrate, fiber cloth substrate, polyimide (PI) substrate, crystalline silicon wafer, flexible wiring board, ceramic substrate, PCB substrate, and the like. Then, the conductive line is subjected to a drying heat treatment process; wherein the heat treatment temperature ranges from 80 to 200 ° C, and the heat treatment time is from 5 to 240 minutes. The drying heat treatment process includes single-stage drying or multi-stage drying. For example, referring to the microscopic morphology of the conductive line prepared by the conductive ink of Embodiment 2 of FIG. 1, the two-dimensional flake graphene and the metal nanobelt material are combined, and the metal nanobelt is electrically conductive with graphene and micro-nano carbon. The surface contact between the fillers replaces the point contact of the common metal nanoparticles with the conductive filler, and the flat strip shape of the metal nanobelts is used to form a wire network between the different conductive fillers to ensure excellent electrical conductivity of the conductive wires. The performance of the product was tested (tested by the four-probe method, the film thickness of the test film was 25 um, and the measured resistance was the average of the three film samples). The comparison results are shown in Table 7:
表7 本发明实施例1-6的产品性能检测数据对比结果Table 7 Comparison results of product performance test data of Examples 1-6 of the present invention
实施例Example 导电剂含量(％)Conductive agent content (%) 方阻(Ω/□)Square resistance (Ω/□)
实施例1Example 1 3030 0.050.05
实施例2Example 2 3030 0.040.04
实施例3Example 3 3232 0.080.08
实施例4Example 4 21twenty one 0.070.07
实施例5Example 5 2727 0.060.06
实施例6(对比例)Example 6 (Comparative) 4040 1212
上述实施例仅用来进一步说明本发明的一种石墨烯/金属纳米带复合导电油墨及其制备方法和应用，但本发明并不局限于实施例，凡是依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均落入本发明技术方案的保护范围内。The above embodiments are only used to further illustrate a graphene/metal nanobelt composite conductive ink of the present invention, and a preparation method and application thereof, but the present invention is not limited to the embodiment, and the above embodiments are in accordance with the technical essence of the present invention. Any simple modifications, equivalent changes, and modifications made within the scope of the present invention fall within the scope of the present invention.

Claims (15)

  1. 一种石墨烯/金属纳米带复合导电油墨，其特征在于：所述油墨包括以下重量份的组份：石墨烯1～20份，金属纳米带1～5份，纳米导电炭黑1～20份，石墨0～20份，高分子粘接剂1～25份，助剂0.5～10份，溶剂10～70份；其中所述金属纳米带的带宽小于200nm，带长为1～50μm，长宽比为10:1～2500:1，厚度小于100nm。A graphene/metal nanobelt composite conductive ink, characterized in that the ink comprises the following components by weight: 1-20 parts of graphene, 1-5 parts of metal nanobelts, 1-20 parts of nano conductive carbon black 0 to 20 parts of graphite, 1 to 25 parts of polymer binder, 0.5 to 10 parts of auxiliary agent, and 10 to 70 parts of solvent; wherein the metal nanobelt has a bandwidth of less than 200 nm, a belt length of 1 to 50 μm, and a length and a width. The ratio is 10:1 to 2500:1 and the thickness is less than 100 nm.
  2. 根据权利要求1所述的石墨烯/金属纳米带复合导电油墨，其特征在于：所述石墨烯、金属纳米带、纳米导电炭黑和石墨的总质量为所述油墨总质量的10～35％。The graphene/metal nanobelt composite conductive ink according to claim 1, wherein the total mass of the graphene, the metal nanobelt, the nanoconductive carbon black and the graphite is 10 to 35% of the total mass of the ink. .
  3. 根据权利要求1所述的石墨烯/金属纳米带复合导电油墨，其特征在于：所述金属纳米带包括银纳米带、铜纳米带、钯纳米带、镍纳米带、经过表面有机改性或金属氧化物改性处理的多组分金属纳米带中的至少一种。The graphene/metal nanobelt composite conductive ink according to claim 1, wherein the metal nanobelt comprises silver nanobelts, copper nanobelts, palladium nanoribbons, nickel nanobelts, surface organic modified or metal At least one of the oxide-modified multicomponent metal nanoribbons.
  4. 根据权利要求1所述的石墨烯/金属纳米带复合导电油墨，其特征在于：所述金属纳米带的带宽为10～100nm，带长为2～10μm，长宽比为20:1～200:1，厚度为5～50nm。The graphene/metal nanobelt composite conductive ink according to claim 1, wherein the metal nanobelt has a bandwidth of 10 to 100 nm, a tape length of 2 to 10 μm, and an aspect ratio of 20:1 to 200: 1, the thickness is 5 ~ 50nm.
  5. 根据权利要求1所述的石墨烯/金属纳米带复合导电油墨，其特征在于：所述石墨烯为单层或2～5层石墨烯、还原氧化石墨烯、石墨烯纳米片、石墨烯纳米带中的至少一种，其片层大小为2～50μm，其厚度为1～10nm；其中所述还原氧化石墨烯的碳氧比为1000:1～2:1。The graphene/metal nanobelt composite conductive ink according to claim 1, wherein the graphene is a single layer or 2 to 5 layers of graphene, reduced graphene oxide, graphene nanosheets, graphene nanoribbons At least one of the layers has a sheet size of 2 to 50 μm and a thickness of 1 to 10 nm; wherein the reduced graphene oxide has a carbon to oxygen ratio of 1000:1 to 2:1.
  6. 根据权利要求1所述的石墨烯/金属纳米带复合导电油墨，其特征在于：所述高分子粘接剂为热固性胶粘剂、热塑性胶粘剂、橡胶型胶粘剂或复合型胶粘剂；所述热固性胶粘剂以含有反应性基团的热固性树脂为主体制成，热塑性胶粘剂以线型高分子结构的热塑性树脂为主体，复合型胶粘剂以热固性树脂和合成橡胶或热塑性树脂为主体制成。The graphene/metal nanobelt composite conductive ink according to claim 1, wherein the polymer binder is a thermosetting adhesive, a thermoplastic adhesive, a rubber adhesive or a composite adhesive; and the thermosetting adhesive contains a reaction. The thermosetting resin of the group is mainly prepared, and the thermoplastic adhesive is mainly composed of a thermoplastic resin having a linear polymer structure, and the composite adhesive is mainly composed of a thermosetting resin, a synthetic rubber or a thermoplastic resin.
  7. 根据权利要求6所述的石墨烯/金属纳米带复合导电油墨，其特征在于：所述高分子树脂包括环氧树脂、酚醛树脂、羟基氯醋树脂、羧基氯醋树脂、丙烯酸树脂、 三元羟基树脂、聚酯树脂、乙基纤维素、丙基纤维素、聚氨酯树脂、聚偏氟乙烯树脂、氯丁橡胶、丁腈橡胶等高分子粘接剂树脂中的至少一种以及聚酰胺蜡、氢化蓖麻油等防沉淀剂树脂中的至少一种。The graphene/metal nanobelt composite conductive ink according to claim 6, wherein the polymer resin comprises an epoxy resin, a phenol resin, a hydroxychloroacetic resin, a carboxy chloroacetate resin, an acrylic resin, and a ternary hydroxyl group. At least one of a polymer binder resin such as a resin, a polyester resin, an ethyl cellulose, a propyl cellulose, a urethane resin, a polyvinylidene fluoride resin, a chloroprene rubber, or a nitrile rubber, and a polyamide wax, hydrogenated At least one of anti-precipitant resins such as castor oil.
  8. 根据权利要求1所述的石墨烯/金属纳米带复合导电油墨，其特征在于：所述溶剂为醇类溶剂、酯类溶剂、芳香烃类溶剂、酮类溶剂、醚类溶剂以及脂肪族烷烃类溶剂中的至少一种。The graphene/metal nanobelt composite conductive ink according to claim 1, wherein the solvent is an alcohol solvent, an ester solvent, an aromatic hydrocarbon solvent, a ketone solvent, an ether solvent, and an aliphatic alkane. At least one of the solvents.
  9. 根据权利要求8所述的石墨烯/金属纳米带复合导电油墨，其特征在于：所述溶剂包括乙醇、异丙醇、正丁醇、松油醇、磷酸三丁酯、丙二醇甲醚丙酸酯、二乙二醇二苯甲酸酯、N-甲基吡咯烷酮、二甲基甲酰胺、二甘醇***乙酯、乙二醇二缩水甘油醚、乙二醇丁醚乙酸酯、DBE、丙二醇甲醚醋酸酯、乙二醇***醋酸酯、甲苯、二甲苯、丙酮、环己酮、乙二醇丁醚、丙二醇丁醚、甲基环己烷、正己烷、#150汽油的至少一种。The graphene/metal nanobelt composite conductive ink according to claim 8, wherein the solvent comprises ethanol, isopropanol, n-butanol, terpineol, tributyl phosphate, propylene glycol methyl ether propionate. , diethylene glycol dibenzoate, N-methylpyrrolidone, dimethylformamide, diethylene glycol ethyl ether ethyl ester, ethylene glycol diglycidyl ether, ethylene glycol butyl ether acetate, DBE, propylene glycol At least one of methyl ether acetate, ethylene glycol ethyl ether acetate, toluene, xylene, acetone, cyclohexanone, ethylene glycol butyl ether, propylene glycol butyl ether, methyl cyclohexane, n-hexane, and #150 gasoline.
  10. 根据权利要求1所述的石墨烯/金属纳米带复合导电油墨，其特征在于：还包括重量份为0.1～5份的金属纳米颗粒，所述金属纳米颗粒是银颗粒、铜颗粒、钯颗粒、镍颗粒中的至少一种，粒径为10～100nm。The graphene/metal nanobelt composite conductive ink according to claim 1, further comprising 0.1 to 5 parts by weight of metal nanoparticles, wherein the metal nanoparticles are silver particles, copper particles, palladium particles, At least one of the nickel particles has a particle diameter of 10 to 100 nm.
  11. 根据权利要求1所述的石墨烯/金属纳米带复合导电油墨，其特征在于：所述助剂包括消泡剂、附着力促进剂、润湿剂、流平剂、分散剂、乳化剂、催干剂中的至少一种。The graphene/metal nanobelt composite conductive ink according to claim 1, wherein the auxiliary agent comprises an antifoaming agent, an adhesion promoter, a wetting agent, a leveling agent, a dispersing agent, an emulsifier, and a reminder. At least one of the dry agents.
  12. 一种权利要求11所述的石墨烯/金属纳米带复合导电油墨的制备方法，其特征在于包括以下步骤：A method for preparing a graphene/metal nanobelt composite conductive ink according to claim 11, comprising the steps of:
    (a)导电填料的预处理：将石墨烯、炭黑、石墨、金属纳米带按照预设比例称量后混合均匀，并在混合过程中添加分散剂助剂进行改性处理；(a) Pretreatment of conductive filler: The graphene, carbon black, graphite, and metal nanobelts are weighed according to a preset ratio and uniformly mixed, and a dispersant auxiliary agent is added for modification treatment during the mixing process;
    (b)有机相的配制：将预设份量的高分子粘接剂树脂与防沉淀剂树脂置于加热反应容器中，再添加溶剂润湿树脂，将混合物加热至40～100℃，恒温加热搅拌0.5～12 小时，确保树脂完全溶解后，将消泡剂、附着力促进剂、润湿剂、流平剂、乳化剂、催干剂助剂中的至少一种添加到有机液相中，搅拌至分散溶解均一，得到有机相溶液，冷却待用；(b) Preparation of organic phase: placing a predetermined amount of polymer binder resin and anti-precipitant resin in a heating reaction vessel, adding a solvent to wet the resin, heating the mixture to 40-100 ° C, heating at a constant temperature 0.5 to 12 hours, after ensuring complete dissolution of the resin, at least one of an antifoaming agent, an adhesion promoter, a wetting agent, a leveling agent, an emulsifier, and a drier adjuvant is added to the organic liquid phase, and stirred. To disperse and dissolve uniformly, obtain an organic phase solution, and cool for use;
    (c)导电油墨初级产品的制备：将(a)中预处理的导电填料缓慢添加到(b)中的有机相溶液中，边添加边搅拌，确保导电填料粉体完全润湿、分散到有机相溶液中，待粉体分散均一时，得到导电油墨初级产品；(c) Preparation of conductive ink primary product: slowly add the conductive filler pretreated in (a) to the organic phase solution in (b), and stir while adding to ensure that the conductive filler powder is completely wetted and dispersed to the organic In the phase solution, when the powder is uniformly dispersed, a conductive ink primary product is obtained;
    (d)导电油墨初级产品的加工处理：将(c)中的导电油墨初级产品置于高速剪切分散机的容器中进行固液高速剪切分散混合或采用球磨机高速研磨混合，然后转移至三辊研磨中研磨至细度达到5～10μm，得到均质导电油墨的最终产品。(d) Processing of conductive ink primary product: The conductive ink primary product in (c) is placed in a container of a high-speed shear disperser for solid-liquid high-speed shear dispersion mixing or high-speed grinding mixing using a ball mill, and then transferred to three Grinding to a fineness of 5 to 10 μm in roll grinding gives a final product of a homogeneous conductive ink.
  13. 权利要求1～11任一项所述的石墨烯/金属纳米带复合导电油墨于印制导电线路上的应用。Use of the graphene/metal nanobelt composite conductive ink according to any one of claims 1 to 11 for printing a conductive line.
  14. 根据权利要求13所述的应用，其特征在于：所述石墨烯/金属纳米带复合导电油墨通过丝网印刷、柔性版印刷、凹版印刷或喷墨打印印制导电线路于基材上。The use according to claim 13, wherein the graphene/metal nanobelt composite conductive ink is printed on the substrate by screen printing, flexographic printing, gravure printing or ink jet printing.
  15. 根据权利要求14所述的应用，其特征在于：所述印制导电线路还包括将印制在基材上的导电线路进行烘干热处理的工艺步骤；其中的热处理温度范围为80～200℃，热处理时间为5～240分钟。The application according to claim 14, wherein the printed conductive circuit further comprises a process step of drying and heat-treating the conductive trace printed on the substrate; wherein the heat treatment temperature ranges from 80 to 200 ° C, The heat treatment time is 5 to 240 minutes.
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